Substituted acetonaphthone perfume compositions

ABSTRACT

Described are hexahydrotetramethyl acetonaphthones and mixtures of such substituted acetonaphthones having the generic formula: ##STR1## wherein one of the dashed lines is a carbon-carbon double bond and each of the other of the dashed lines is a carbon-carbon single bond, and, specifically, the novel isomer having the structure: ##STR2## and processes for the preparation of such mixtures and said novel isomer, as well as a known single component of said mixtures and compounds. 
     The products produced are useful as vetiver ingredients in perfumes and perfumed articles.

This application is a divisional application of United StatesApplication for Letters Patent, Ser. No. 740,890, filed on Nov. 11,1976, now U.S. Pat. No. 4,076,749, issued on Feb. 28, 1978.

BACKGROUND OF THE INVENTION

Materials which can provide aromas with sweet woody, citrusy, vetiver,musky, woody/peppery, woody/leathery, hay and green nuances and/or woodyfragrance notes are known in the art of perfumery. Natural materialswhich provide such fragrances and contribute desired nuances toperfumery compositions, such as natural vetiver oil, are frequentlydifficult to obtain and/or are high in cost or vary in quality from onebatch to another and/or are generally subject to the usual variations ofnatural products.

There is accordingly a continuing effort to find synthetic materialswhich will replace the essential fragrance notes provided by naturalessential oils or compositions thereof having a vetiver aroma.Unfortunately, many of these synthetic materials either have the desirednuances only to a relatively small degree or else contribute undesirableor unwanted odor to the composition. The search for materials which canprovide a more refined vetiver fragrance has been difficult andrelatively costly in the areas of both natural products and syntheticproducts.

Acetonaphthones, particularly octahydro acetonaphthone, are known inperfumery particularly for providing amber or fruity amber fragrancenotes which do not discolor with age. Thus, U.S. Pat. No. 3,911,018,issued on Oct. 7, 1975, covers an isomer of octahydrotetramethylacetonaphthone having the structure: ##STR3## wherein the dashed linesrepresent methyl groups "cis" to one another.

United States Pat. No. 3,911,018 also covers processes for producingisomer mixtures of octahydro-2',3',8',8'-tetramethyl-(2' or3')-acetonaphthone having the generic formula: ##STR4## wherein one ofthe wavy lines is a carbon-carbon double bond and the other of the wavylines represent carbon-carbon single bonds. The mixtures produced by theprocesses of United States Pat. No. 3,911,018 contain from 70 molepercent up to 99 mole percent of compounds having the generic structure:##STR5## Such a generic structure includes individual compounds havingan acetyl group at the 2' position, compounds having an acetyl group atthe 3' position and mixtures of such compounds. The generic structuresset forth above also include geometric isomers wherein the acetyl groupis cis to the methyl group on the carbon atom adjacent to that bonded tothe acetyl moiety and where the acetyl group is "trans" to the methylgroup on the carbon atom adjacent to that bonded to the acetyl moiety.Furthermore, the products of U.S. Pat. No. 3,911,018 are indicated to beproduced by means of a two-step reaction:

1. Reacting myrcene with 3-methyl-3-penten-2-one either:

a. in the presence of a Lewis acid at temperatures in the range of from0° up to 50° C thereby producing a mixture of geometric isomers whichare Diels-Alder adducts which are alkenyl acetyl dimethyl substitutedcyclohexenes represented by the structure: ##STR6## or: b. reactingmyrcene with 3-methyl-3-penten-2-one without using a catalyst attemperatures in the range of 120° C up to 180° C forming a mixture ofisomers (including geometric isomers) of alkenyl acetyl dimethylsubstituted cyclohexenes having the generic structure: ##STR7##

2. Cyclizing the resulting substituted cyclohexenes (Diels-Alderadducts) by means of heating same in the presence of phosphoric acid ordilute sulfuric acid (50-80%) or boron trifluoride or complexes thereof,e.g., boron trifluoride etherate.

Kagi, et al, Journal of the Society of Cosmetic Chemists, (GreatBritain), 1973, pages 1-14, "Catalyzed Diels-Alder Reactions in theSynthesis of Perfumery Materials", discloses a synthesis of one of theisomers capable of being produced by the processes of the invention,which isomer has the structure: ##STR8## by means of reacting myrceneand 3-bromo-4-methylpent-3-ene-2-one to give the bromo adduct having thestructure: ##STR9## and then dehydrobrominating the said bromo adduct togive the dienone. Kagi, et al, reports that this particular isomer has"a very powerful, musk-ambergris odour" on page 10. The novel isomer aswell as the mixture of isomers produced by the instant invention haveproperties which are advantageous and unexpected with respect to theparticular isomer of Kagi, et al.

In addition, British Pat. No. 896,039 entitled "Method of ProducingDerivatives of the 1,1-Dimethyl-octahydronaphthalene Series" disclosesthe generic process: ##STR10## wherein R₂, R₃ and R₄ are disclosed to bethe same or different and hydrogen or alkyl and R₁ is disclosed to behydroxy, alkyl or alkoxy. The British patent discloses this process tobe useful for producing products "resembling the well known class ofviolet perfumes". Indeed, Example 5 of the British patent alleges thatthe compound 1,1,6,6-Tetramethyl-7-ketomethyl-Octalin produced by (1)reacting myrcene and mesityl oxide thermally followed by (2) subsequentcyclization, has a pleasant "woody ambergris smell". However, arepetition of the teachings of this British patent gives rise to thefollowing results:

STRUCTURE OF COMPOUND ##STR11## NAME:

1',2',3',4',5',6',7',8'-octahydro-8',8'(and5',5')dimethyl-2'-naphthaldehyde

PERFUME PROPERTIES:

Green, fruity

STRUCTURE OF COMPOUND ##STR12## NAME:

1',2',3',4',5',6',7',8'-octahydro-2',8',8'(and 2',5',5')trimethyl-2',naphthaldehyde

PERFUME PROPERTIES:

Green floral, fruity

STRUCTURE OF COMPOUND ##STR13## NAME:

1',2',3',4',5',6',7',8'-octahydro-3',8',8'(and3',5',5')trimethyl-2'-naphthaldehyde

PERFUME PROPERTIES:

Green, buttery, woody

STRUCTURE OF COMPOUND ##STR14## NAME:

1',2',3',4',5',6',7',8'-octahydro-5',5'(and8',8')-dimethyl-2'-acetonaphthone

PERFUME PROPERTIES:

Ionone-like

STRUCTURE OF COMPOUND ##STR15## NAME:

1',2',3',4',5',6',7',8'-octahydro-3',3',8',8'(and3',3',5',5')-tetramethyl-2'-acetonaphthone

PERFUME PROPERTIES:

Yeasty, valerian-like

STRUCTURE OF COMPOUND ##STR16## NAME:

1',2',3',4',5',6',7',8'-octahydro-2',8',8'(and2',5',5')-trimethyl-2'-acetonaphthone

PERFUME PROPERTIES:

Fruity, woody, pineapple-like

STRUCTURE OF COMPOUND ##STR17## NAME:

1',2',3',4',5',6',7',8'-octahydro-3',5',5'(and3',8',8')-trimethyl-2'-propionaphthone

PERFUME PROPERTIES:

Fruity, woody, pineapple-like and ionone like

STRUCTURE OF COMPOUND ##STR18## NAME:

1',2',3',4',5',6',7',8'-octahydro-3',5',5'-(and3',8',8')-trimethyl-2'-acetonaphthone

PERFUME PROPERTIES:

Low keyed woody, fruity

In addition to the above-mentioned British patent, the above statedsequence of:

1. Diels-Alder Reaction to form Diels-Alder adducts followed by

2. Cyclization of the Diels-Alder adducts is disclosed in detail byOhloff Ann. 606,100 (1957).

Further, cyclization reactions of Diels-Alder adducts of myrcene and adienophile are set forth in U.S. Pat. No. 3,076,022. This patentdiscloses interalia, preparation of the thermal Diels-Alder adduct ofmyrcene and methyl isopropenyl ketone and subsequent acid cyclization toa product said to possess "an intense ambergris-like note". Repetitionof the process as disclosed gave rise to a product possessing fruity,woody, pineapple notes rather than an ambergris-like note.

Ohloff [Chemistry of Odoriferous and Flavoring Substances] pp. 185-240(at page 192) Fortschritte und der Chemischen Forschung Vol. 12, Part 2,1969, discloses a compound having the structure: ##STR19## Ohloffindicates that materials of this nature have "resiny odors" likeolibanum, with amber type undertones.

However, none of the prior art substituted acetonaphthone compoundspossess aromas having sweet woody, vetiver, citrusy, musky,woody/peppery, woody/leathery, hay and green nuances and/or woodyfragrance notes of the compounds of our invention.

2-Acetyl-3,4,4a,5,6,7-hexahydro-4a,8-dimethylnaphthalene having thestructure: ##STR20## has been determined to occur naturally in vetiveroil. It has a sweet, woody, musky and herbal aroma, from a perfumerystandpoint, and a musky, oriental, woody, vetiver aroma profile and amusky, oriental, woody, vetiver, astringent flavor character, havingpotential uses in blueberry and pear flavors. Although having similarfunctional groups of the compound of the instant invention, thestructure and fragrance profiles are different in kind from the mixturesand isomers of the instant invention.

United States Pat. No. 3,845,135, issued on Oct. 29, 1974 is directed tothe manufacture of beta ionones but erroneously sets forth a structureat column 1, line 65 thereof as follows: ##STR21## Obviously a printingerror occurred showing a bond between the group "R² " and a methylgroup.

Other acetyl hexahydro naphthalenes are known, but the structures ofsuch compounds are different in kind from those of the instantinvention. Thus, an article by Watt and Corey in Tetrahedron Letters,No. 46, pages 4651-4654, 1972, discloses compounds having thestructures: ##STR22##

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the NMR spectrum for fraction 7 produced according toExample II (A), which consists of a compound having the structure:##STR23##

FIG. 2 represents the Infrared spectrum for fraction 7 of Example II(A), which consists of a compound having the structure: ##STR24##

FIG. 3 represents the NMR spectrum for the compound produced accordingto Example II (B) which has the structure: ##STR25##

FIG. 4 represents the Infrared spectrum for the compound producedaccording to Example II (B) which has the structure: ##STR26##

FIG. 5 represents the NMR spectrum for the GLC trapping identified as"peak 1" produced according to Example II (C) and which consistsessentially of a compound having the structure: ##STR27##

FIG. 6 represents the Infrared spectrum for the GLC trapping identifiedas "peak 1" produced according to Example II (C) and which consistsessentially of a compound having the structure: ##STR28##

FIG. 7 represents the NMR spectrum for the GLC trapping of Example II(C) identified as "peak 2" and which consists of the novel isomer havingthe structure: ##STR29##

FIG. 8 represents the Infrared spectrum for the GLC trapping of ExampleII (C) identified as "peak 2" and which consists of a compound havingthe structure: ##STR30##

FIG. 9 represents the NMR spectrum of the chlorinated acetyl octahydronaphthalene derivative produced according to Example III (A) having thestructure: ##STR31##

FIG. 10 represents the Infrared spectrum for the compound producedaccording to Example III (A) which is a chlorinated acetyl octahydronaphthalene derivative having the structure: ##STR32##

FIG. 11 represents the NMR spectrum for2-acetyl-3,4,4a,5,6,7-hexahydro-4a,8-dimethylnaphthalene producedaccording to Example XI and which was isolated from vetiver oil.

FIG. 12 represents the Infrared spectrum for2-acetyl-3,4,4a,5,6,7-hexahydro-4a,8-dimethylnaphthalene producedaccording to Example XI and which was isolated from vetiver oil.

THE INVENTION

This invention relates to a genus of substituted hexahydroacetonaphthones having the generic structure: ##STR33## wherein one ofthe dashed lines is a carbon-carbon double bond and each of the other ofthe dashed lines is a carbon-carbon single bond as individual compoundsand as mixtures. Such compounds are useful as fragrance ingredients forperfumes and perfumed articles including soaps, detergents, cosmeticpowders and colognes. More particularly, these compounds have aromaswith sweet woody, citrusy, vetiver-like, musky, woody/peppery,woody/leathery, hay and green nuances and/or woody fragrance notes.

The mixtures and isomers of our invention, including the novel isomerhaving the structure: ##STR34## as well as the known individual isomericcomponent of said mixtures, are produced by first forming3-chloromesityl oxide from chlorine and mesityl oxide and then reactingthe 3-chloromesityl oxide with myrcene via a Diels-Alder reactionthereby forming a chlorine containing Diels-Alder adduct. The chlorinecontaining Diels-Alder adduct may then either:

(i) be dehydrochlorinated to form an acetyl conjugated cyclohexadienewhich may be cyclized to form a mixture of compounds represented by thestructure: ##STR35## wherein one of the dashed lines is a carbon-carbondouble bond and each of the other of the dashed lines is a carbon-carbonsingle bond; or

(ii) it may first be cyclized to form an acetyl chlorinatedoctahydronaphthalene which may then be dehydrochlorinated to form acomposition containing a substantial quantity of the known isomer havingthe structure: ##STR36##

When the mixture of isomers is formed as in method (i), these isomersmay, if desired, be separated by means of preparative vapor phasechromatography. As a result of such a separation, the isomer having thestructure: ##STR37## is produced: The reaction sequence is illustratedas follows: ##STR38##

The reaction of chlorine with mesityl oxide results instantly in theformation of a dichloro derivative having the structure: ##STR39##

The reaction is carried out in the presence of a solvent such asdimethyl formamide and optionally in the presence of a base such assodium carbonate or sodium acetate. The mole ratio of chlorine:mesityloxide is greater than 1 in order to insure completion of reaction. Whenbase is used the mole ratio of base:chlorine is preferably about 1:1.The procedure is related to that of Pauley and Lieck, Ber., 33,500(1900), but the use of dimethyl formamide represents an improvementover the conditions set forth in the literature.

After the dihalogen compound is formed, it is dehydrohalogenated bymeans of heating the reaction mixture at a temperature in the range of90°-120° C, preferably 100° C, thereby forming 3-chloromesityl oxide.The reaction of the 3-chloromesityl oxide with myrcene, a Diels-Alderreaction requires the use of one of a specific group of Friedel Craftstype catalysts, namely, stannic chloride or ethyl aluminum dichloride.Aluminum chloride does not give rise to the desired results. The moleratio of myrcene:3-chloromesityl oxide is preferably near 1:1, althougheither reagent may be used in excess without harming the yield of thedesired chlorine containing Diels-Alder reaction product. Thus, the moleratio of myrcene:3-chloromesityl oxide may vary from 10:1 up to 1:10without any variation in the yield of chlorine containing Diels-Alderreaction product. The mole ratio of Friedel Craftscatalyst:3-chloromesityl oxide is preferably between 0.01:1 and 1:1 withthe most preferred range being from 0.05:1 to 0.1:1. The Diels-Alderreaction may be carried out at a temperature of between 0° and 100° Cwith the preferred temperature of reaction being 45°-55° C. TheDiels-Alder reaction is preferably carried out in an inert solvent,which may be either benzene, toluene or xylene or a chlorinatedhydrocarbon such as methylene dichloride and chloroform.

The dehydrohalogenation of the chlorine containing Diels-Alder reactionproduct in order to form the acetyl conjugated cyclohexadiene takesplace in the presence of a polar, aprotic solvent such as dimethylformamide, dimethyl acetamide, N-methyl pyrrolidinone, hexamethylphosphoramide or pyrrole-N-carboxaldehyde. It is also required that thisreaction take place in the presence of a base such as calcium carbonate,lithium carbonate, magnesium carbonate, calcium oxide, lithium oxide ormagnesium oxide. The temperature of reaction is between 120°-250° C,with a preferred temperature range of 150°-195° C. The mole ratio ofbase:chlorine containing Diels-Alder adduct is between 0.5:1 and 5:1,with a range of 0.5:1 up to 1:1 being preferred.

Similar conditions are effective for dehydrohalogenation of thechlorinated acetyl octahydronaphthalene derivative having the structure:##STR40## in order to form a composition containing a substantialquantity of the isomer having the structure: ##STR41## The cyclizationreactions for: (i) cyclizing the chlorine containing Diels-Alder adducthaving the structure: ##STR42## (ii) cyclizing the acetyl conjugatedcyclohexadiene having the structure: are similar. The cyclizationreactions are accomplished by heating the compound to be cyclizedpreferably with a mixture of an acid such as phosphoric acid, dilutedsulfuric acid, boron trifluoride or boron trifluoride etherate in thepresence of a solvent. The amount of acid cyclization agent may varyfrom 10 up to 100 weight percent based on the weight of the compound tobe cyclized. Preferably, the weight percent of acid depends upon theparticular acid used. For example, when using phosphoric acid, theweight percent should be between 40 and 100 weight percent. Preferably,an inert solvent having a boiling point at or about the desired reactiontemperature is used in the cyclization reaction. The reactiontemperature may be anywhere between 30° C and the reflux temperature ofthe reaction mixture. The preferred reaction temperature range isbetween 40° C and 60° C for reaction (ii) and between 70° C and 100° Cfor reaction (i) and toluene is the preferred solvent. The quantity ofsolvent used in the cyclization reaction may vary from 0 weight percentup to 100 weight percent based on the amount of compound being cyclized.It is preferred to use approximately 25 to 50 weight percent of solvent.In the cyclization reaction, the order of mixing reagents and solventsis not critical.

When a mixture of isomers is prepared having the generic formula:##STR43## wherein one of the dashed lines is a carbon-carbon double bondand each of the other of the dashed lines is a carbon-carbon singlebond, such mixtures can be used "as is" or it may be further purified byusing fractional distillation techniques, gas chromatography techniques,and/or oximation, followed by recovery of the purified product from theoxime.

One or more of the hexahydrotetramethyl acetonaphthone derivatives ofour invention (including the novel isomer having the structure:##STR44## and one or more auxiliary perfume ingredients, including, forexample, alcohols, aldehydes, ketones, terpenic hydrocarbons, nitriles,esters, lactones, natural essential oils and synthetic essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferably invetiver fragrances. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lead a particular note to theperfume throughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olefactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or morehexahydrotetramethyl acetonaphthone derivative(s) of our invention canbe used to alter, modify or enhance the aroma characteristics of aperfume composition, for example, by utilizing or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of hexahydrotetramethyl acetonaphthone derivative(s) of ourinvention which will be effective in perfume compositions as well as inperfumed articles and colognes depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.01%of hexahydrotetramethyl acetonaphthone derivative(s) or even less (e.g.,0.005%) can be used to impart a vetiver aroma with sweet woody, citrusy,musky, woody/peppery, woody/leathery, hay and green nuances to soaps,cosmetics, detergents, powders and colognes. The amount employed canrange up to 70% of the fragrance components and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The hexahydrotetramethyl acetonaphthone derivative(s) of our inventionare useful [taken along or together with other ingredients in perfumecompositions] as (an) olfactory component (s) in detergents and soaps,space odorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations, such as creams, deodorants, hand lotions and sunscreens; powders, such as talcs, dusting powders, face powders and thelike. When used as (an) olfactory component(s) as little as 1% ofhexahydrotetramethyl acetonaphthone derivative(s) will suffice to impartan intense aroma with sweet woody, vetiver, citrusy, musky,woody/peppery, woody/leathery, hay and green nuances to vetiverformulations. Although, generally, no more than 60% ofhexahydrotetramethyl acetonaphthone derivative(s), based on the ultimateend product, is required in the perfume composition, amounts ofhexahydrotetramethyl acetonaphthone derivative of up to 95% may be usedin such perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the hexahydrotetramethylacetonaphthone derivative(s). The vehicle can be a liquid such as anon-toxic alcohol, a non-toxic glycol, or the like. The carrier can alsobe an absorbent solid, such as a gum (e.g., gum arabic) or componentsfor encapsulating the composition (such as gelatin).

It will thus be apparent that the hexahydrotetramethyl acetonaphthonederivative(s) of our invention can be utilized to alter, modify orenhance sensory properties, particularly organoleptic properties, suchas flavor(s) and/or fragrance(s) of a wide variety of consumablematerials.

The following examples serve to illustrate our invention and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I (A) PREPARATION OF 3-CHLOROMESITYL OXIDE

Reaction: ##STR45## Procedure:

Into a 12 liter reaction flask equipped with stirrer, condenser,thermometer and gas addition tube, 1963 g (20.0 moles) mesityl oxide,2050 g (25.0 moles) of sodium acetate and 2000 ml dimethyl formamide areplaced. The contents of the flask are cooled to 0° C. At a rapid rateover a 31/2 hour period, while maintaining the reaction mass at 0° C,888 g (25.0 moles) chlorine is added to the reaction mass. The mixtureis then heated to 100° C for a period of 2 hours. Sufficient quantitiesof water are added to the reaction mass to cause it to separate into twophases. The organic phase is washed with two 2000 cc portions of water,and then dried over anhydrous magnesium sulfate, filtered and distilledthrough a 12 × 11/2 stone packed column yielding 1740 grams of product,b.p. 68°-69° C (45 mm Hg).

EXAMPLE I (B) PREPARATION OF 3-CHLOROMESITYL OXIDE

A 22 liter three necked reaction flask equipped with stirrer,thermometer, cooling bath and gas inlet tube is charged with 4900 gramsof mesityl oxide and 2500 ml dimethylformamide. The mixture is stirredat 0°-5° C, as 4438 grams of chlorine is added over a 5 hour period.Nitrogen is then passed through the mixture as it is heated to 100° Cand held at that temperature for 3 hours. The cooled reaction mass iswashed with three volumes of water (methylene chloride is added to aidin separation of the layers). The organic phase is then distilledthrough a 2' × 11/2 inches column packed with porcelain saddles to give3231 grams product, b.p. 70°-80° C (50 mm Hg).

EXAMPLE II (A) DIELS-ALDER REACTION OF MYRCENE WITH 3-CHLOROMESITYLOXIDE

Reaction: ##STR46## Procedure:

Into a 500 cc reaction flask equipped with stirrer, thermometer,addition funnel, heating mantle and nitrogen blanket is placed 13 g of25% ethyl aluminum dichloride in heptane (0.025 moles) and a solution of35 g (0.25 moles) of 3-chloromesityl oxide in 50 ml anhydrous benzene.While maintaining the resulting mixture at a temperature of 4° C, over aperiod of 30 minutes, a solution of 53 g of 85% myrcene (0.30 moles) in50 ml benzene is added. The reaction mass is then allowed to warm toroom temperature and then stirred at a temperature of between 25° and45° C for a period of 5 hours. 250 ml water and 300 ml diethyl ether isthen added to the reaction mass. The organic phase is separated, washedwith water, dried and stripped of solvent. The resulting oil isdistilled through a micro Vigreux column to give 47.0 g product, b.p.112°-123° C (0.8 mm Hg).

Fraction 7, b.p. 120°-123° C (0.8 mm Hg), is analyzed using NMR andInfrared analyses.

The NMR spectrum is set forth in FIG. 1. The Infrared spectrum is setforth in FIG. 2.

The NMR spectrum is as follows:

    ______________________________________                                        δ, ppm                                                                             Assignment                                                         ______________________________________                                        0.97-1.10  gem dimethyl protons                                                                             6H                                              1.60                                                                                      ##STR47##         6H                                              2.46-1.82  CH.sub.2           8H                                              2.36                                                                                      ##STR48##         3H                                              5.08                                                                                      ##STR49##         1H                                              5.27       "cyclic" olefinic                                                             proton             1H                                              ______________________________________                                    

The Infrared spectrum contains the following bands:

810, 1150, 1180, 1200, 1220, 1350, 1365, 1425, 1445, 1700, 1725, 2920,2970 cm⁻¹

EXAMPLE II (B) DEHYDROHALOGENATION OF DIELS-ALDER ADDUCT

Reaction: ##STR50## Procedure:

Into a 250 cc reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed 48 g (0.22 moles) of theDiels-Alder adduct produced according to Example II (A), 125 mlN-methyl-pyrrolidinone and 35 g calcium carbonate. The reaction mass isheated and maintained at 150°-180° C for a period of 1 hour. Thereaction mass is then cooled to room temperature, after which time it isfiltered and the solids washed with diethyl ether. The solution iswashed with water and the aqueous phase is extracted with diethyl ether.The ether extracts are bulked, dried over anhydrous magnesium sulfate,stripped of solvent and distilled through a micro Vigreux column to give28.0 g product, b.p. 122°-128° C (1.0 mm Hg).

NMR and Infrared analyses confirm that the resulting product has thestructure: ##STR51##

The NMR spectrum is set forth in FIG. 3. The Infrared spectrum is setforth in FIG. 4.

The NMR spectrum is as follows:______________________________________δ,ppm Assignment______________________________________1.14 gem dimethylprotons 6H1.62 ##STR52## 6H2.16-2.06 CCH₂ 6H2.24 ##STR53## 3H5.1olefinic proton 1H5.806.72 ##STR54##2H______________________________________

The Infrared spectrum contains the following bands:

1205, 1245, 1260, 1350, 1360, 1370, 1380, 1450, 1560, 1635, 1655, 2860,2920, 2950 cm³¹ 1

EXAMPLE II (C) CYCLIZATION OF ACETYL CONJUGATED CYCLOHEXADIENEDERIVATIVE

Reaction: ##STR55## Procedure:

Into a 100 ml reaction flask equipped with stirrer, reflux condenser,thermometer and heating mantle are placed 25 g of the acetyl conjugatedcyclohexadiene derivative produced according to Example II (B), 25 g 85%phosphoric acid and 10 g of toluene.

The reaction mass is stirred at a temperature of 25°-35° C for a periodof 2 hours, after which time it is heated at 50°-65° C over a period of11/2 hours. At the end of this period of time, the reaction mass iscooled to room temperature and two volumes of water are added. Theaqueous phase is separated from the organic phase and then extractedwith an equal volume of toluene. The combined organic layers are washedwith water, aqueous sodium bicarbonate and then washed neutral withwater. The organic phase is then stripped of solvent (crude weight: 30g) and distilled on a 4 inch micro Vigreux column yielding 19.0material, b.p. 126°-145° C (0.8-0.9 mm Hg).

Fraction 4 is confirmed to be a mixture of compounds having thestructure: ##STR56## wherein one of the dashed lines is a carbon-carbondouble bond and each of the other of the dashed lines is a carbon-carbonsingle bond by NMR and Infrared analyses.

The components of fraction 4 are separated using preparative GLC (6' ×1/4 inch Carbowax 20M column). Peak 1 is confirmed by NMR and Infraredanalyses to have the structure: ##STR57## Peak 2 is confirmed by NMR andInfrared analyses to have the structure: ##STR58## Peak 1 is describedas having a woody, musky note and peak 2 is described as having a woody,peppery note. The entire mixture in fraction 4 has a sweet, woody,herbal, vetiver aroma with a citrus, vetivone undertone. Peak 3 has awoody, leathery, "cymene" note.

FIG. 5 illustrates the NMR spectrum for peak 1. FIG. 6 illustrates theInfrared spectrum for peak 1.

The NMR analysis for peak 1 is asfollows:______________________________________δ, ppmAssignment______________________________________1.04 gem dimethylprotons 6H1.12 gem dimethyl protons 6H1.56 CH₂ 4H1.98 CCH₂ 4H2.30##STR59## 3H6.80 olefinic proton1H______________________________________

The Infrared spectrum of peak 1 contains the following bands:

1195, 1240, 1355, 1370, 1450, 1560, 1640, 1655, 2860, 2900, 2920, 2950cm⁻¹

FIG. 7 illustrates the NMR spectrum for peak 2. FIG. 8 illustrates theInfrared spectrum for peak 2.

The NMR analysis for peak 2 is asfollows:______________________________________δ, ppmAssignment______________________________________0.721.101.22 gemdimethyl protons 12H1.261.30-1.041.50 CH₂ 4H2.00 CCH₂ 2H2.32 ##STR60##3H2.60 ##STR61## 1H5.16 olefinic proton 1H6.78 ##STR62##1H______________________________________

The Infrared spectrum of peak 2 contains the following bands:

885, 1210, 1230, 1345, 1410, 1710, 2830, 2860, 2920, 2950 cm⁻¹

EXAMPLE III (A) PREPARATION OF CHLORINATED ACETYL OCTAHYDRO NAPHTHALENEDERIVATIVE BY CYCLIZATION OF CHLORINATED DIELS-ALDER ADDUCT

Reactions: ##STR63## Procedure:

Into a 3 liter reaction flask equipped with stirrer, thermometer,condenser, dropping funnel and nitrogen inlet is placed 202 g of tolueneand 52.0 g (0.40 moles) of ethyl aluminum dichloride. 53.0 g (4.0 moles)of alphachloromesityl oxide, prepared according to Example I (A), isthen added and the resulting solution is heated to 45° C. While stirringthe reaction mass at 45° C, 640 g of 85% myrcene is added dropwise overa period of 1 hour. The reaction mass is then stirred at 45° C for aperiod of 2 hours and then monitored by GLC (conditions: SF 96 column,programmed at 100°-220° C at 8° C per minute). Another 100 g of 85%myrcene (total myrcene: 740 g; 5.44 moles) is added to the reaction massand the temperature of the reaction mass is raised to 60° C andmaintained at that temperature for 21/2 hours.

1270 g (12.9 moles) of phosphoric acid is then added to the reactionmass over a 30 minute period, while maintaining the temperature at25-30° C. The reaction mass is stirred at 60° C for 8 hours and thencooled to room temperature.

1 Liter of water is added to the reaction mass and the resulting mixtureis stirred for 15 minutes. The reaction mass is then extracted with two500 cc portions of diethyl ether and the ether extracts are combinedwith two 300 cc portions of saturated sodium bicarbonate, dried overanhydrous sodium sulfate and distilled without fractionation to yield600 g of product, which is confirmed by NMR and Infrared analyses tohave the structure: ##STR64##

FIG. 9 illustrates the NMR spectrum for this chlorinated acetyloctahydronaphthalene derivative. FIG. 10 illustrates the Infraredspectrum for said chlorinated acetyl octahydronaphthalene derivative.

The NMR analysis is as follows:______________________________________δ,ppm Assignment______________________________________0.98 gem dimethylprotons 6H1.00, 1.09 gem dimethyl protons 6H2.24-1.26 CH₂ 8H2.42##STR65## 3H______________________________________

The Infrared spectrum contains the following bands:

1180, 1205, 1350, 1375, 1420, 1450, 1700, 2920, 2960 cm⁻¹

EXAMPLE III (B) PREPARATION OF HEXAHYDRO ACETONAPHTHONE DERIVATIVE FROMCHLORINATED ACETYL OCTAHYDRONAPHTHALENE DERIVATIVE

Reaction: ##STR66## Procedure:

The 600 g of the chlorinated acetyl octahydronaphthalene derivative,produced in Example III (A), is placed in a 1 liter reaction flask alongwith 500 cc dimethyl formamide and 109.5 g calcium carbonate. Thereaction mass is then refluxed at 140°-150° C for a period of 8 hours.27 g lithium carbonate is then added to the solution and refluxing iscontinued for another 5 hours whereupon GLC analysis indicatescompletion of the reaction (GLC conditions 6' × 1/4 inch 12% SF 96column, programmed at 100°-220° C at 8° C per minute).

250 cc water is then added to the reaction mass and the organic layer isseparated. The aqueous phase is then extracted with two 200 cc portionsof diethyl ether. The extracts are combined with the first organic layerand washed with two 500 cc portions of water, dried over anhydroussodium sulfate, concentrated and distilled without fractionation.

This material is then re-distilled through a 2' × 1 inches Goodloepacked column to give 152 g product, b.p. 100-111° C (0.4-0.5 mm Hg).

GLC, NMR and Infrared analyses confirm that the resulting product hasthe structure: ##STR67##

EXAMPLE IV VETIVER FRAGRANCE

The following mixture isprepared:______________________________________Ingredients Parts byWeight______________________________________Hexahydroacetonaphthonederivative preparedaccording to Example III (B) 50Cedrol25Cedrenyl Acetate 5Isobutyl Quinoline 1Beta Ionone 2Caryophyllene15Eugenol 2 100______________________________________

The hexahydro acetonaphthone derivative prepared according to ExampleIII (B) imparts the rich, deep, green, woody note of vetiver to thisvetiver fragrance.

EXAMPLE V VETIVER FRAGRANCE

The following mixture isprepared:______________________________________Ingredients Parts byWeight______________________________________Hexahydroacetonaphthonederivative preparedaccording to Example II (c) 50Cedrol25Cedrenyl Acetate 5Isobutyl Quinoline 1Beta Ionone 2Caryophyllene15Eugenol 2 100______________________________________

The hexahydro acetonaphthone derivative prepared according to Example II(C) imparts the rich, deep, green, woody note of vetiver to this vetiverfragrance.

EXAMPLE VI PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the hexahydro acetonaphthone derivative producedaccording to Example II (C). It has an excellent vetiver aroma withgreen, sweet woody, citrusy, musky and woody/peppery and woody/leatherynuances.

EXAMPLE VII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with deep, green, grapefruit and woodyaromas (which detergents are produced from Lysine salt of n-dodecylbenzene sulfonic acid, as more specifically described in U.S. Pat. No.3,948,818, issued on Apr. 6, 1976) are prepared containing hexahydroacetonaphthone derivative prepared according to Example IV. They areprepared by adding and homogeneously mixing the appropriate quantity ofhexahydro acetonaphthone derivative in the liquid detergent. Thedetergents all possess a deep, green, musky, grapefruit and woody aroma,the intensity increasing with greater concentrations of hexahydroacetonaphthone derivative.

EXAMPLE VIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

Hexahydro acetonaphthone derivative, prepared according to the processof Example IV is incorporated in a cologne at a concentration of 2.5% in85% aqueous ethanol; and into a handkerchief perfume at a concentrationof 20% (in 95% aqueous ethanol). A distinct and definite deep, green,musky, grapefruit and woody aroma is imparted to the cologne and to thehandkerchief perfume.

EXAMPLE IX PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition of Example V is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use ofthe hexahydro acetonaphthone derivative in the composition of Example Vaffords a distinct and definite deep, green, musky, grapefruit and woodyaroma to the handkerchief perfume and cologne.

EXAMPLE X PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with two grams of thecomposition of Example V until a substantially homogeneous compositionis obtained. The perfumed soap composition manifests an excellentvetiver aroma with rich, deep, green, musky and woody notes.

EXAMPLE XI PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (Lysine salt of n-dodecylbenzene sulfonic acid, as more specifically described in U.S. Pat. No.3,948,818, issued on April 6, 1976) is mixed with 0.70 grams of thecomposition of Example V until a substantially homogeneous compositionis obtained. This composition has an excellent vetiver aroma with rich,deep, green and woody notes.

EXAMPLE XII ISOLATION OF2-ACETYL-3,4,4a,5,6,7-HEXAHYDRO-4a,8-DIMETHYLNAPHTHALENE

A mixture of 300 g of vetivert oil Haiti is intimately admixed with 450ml anhydrous methanol, 45 ml glacial acetic acid and 90 g of Girard-Preagent and placed in a 1 liter reaction flask and refluxed for a periodof 1 hour at 80° C. The resulting mixture is then poured over a mixtureof 1800 g of ice and 27.0 g of aqueous sodium hydroxide solution.

The resulting reaction mass is then placed in a separatory funnel andthe aqueous phase is separated from the oil phase. To the aqueous phaseis added 450 ml concentrated hydrochloric acid and the mixture is keptat room temperature for 90 minutes. The mixture is extracted three timeswith ether and the combined extracts are washed with aqueous sodiumbicarbonate and saturated brine. The organic phase is dried over MgSO₄,concentrated to give 45 g of oil which is then distilled on a spinningband apparatus. A total of 22 fractions are collected. Fraction 12 whichboils at 102° C (0.5 mm Hg) weighs 3.9 g. 3.6 g of this fraction arechromatographed over 100 g of silica gel (deactivated with 5% water),eluting with 2% diethyl ether in isopentane. A 0.8 g portion of thismaterial is re-chromatographed over 50 g deactivated silica gel, elutingwith 1.5% ether in isopentane. From this twice chromatographed materialthe major peak is isolated by preparative GLC on a Carbowax column andis shown by NMR, IR and Mass Spectral analyses to have the followingstructure: ##STR68## The NMR spectrum of this material is set forth inFIG. 11. The Infrared spectrum is set forth in FIG. 12.

The mass spectrum contains the followingions:______________________________________m/e = relative intensity392341 2143 10091 20105 19161 33189 47M20451______________________________________

EXAMPLE XIII SYNTHESIS OF2-ACETYL-3,4,4a,5,6,7-HEXAHYDRO-4a,8-DIMETHYLNAPHTHALENE Part A:Synthesis of trans-8,10-dimethyl(9)octal-2-one

Reaction: ##STR69## Procedure:

Under a nitrogen purge, a mixture of 42 grams sodamide (1.07 moles), 138grams 2,6-dimethyl cyclohexanone (1.1 moles) and 750 ml benzene isrefluxed for a period of 5 hours. A solution of 126 grams (1 mole) of1,3-dichloro-butene in 100 ml benzene is added slowly to the abovereaction mass which is then refluxed for another 4 hours. The mixture iscooled to room temperature, and then 100 ml aqueous 6 molar hydrochloricacid is added. The reaction mixture is then extracted with five 100 mlportions of diethyl ether and the extracts are combined, dried overanhydrous magnesium sulfate and the solvents evaporated, thereby giving205 g of crude reaction product. The resulting material is distilled ona 6 inch silvered column yielding 148.4 g of product, b.p. 75°-78° C(0.1-0.2 mm Hg). The reaction product has the structure: ##STR70##

Part B: Production of 2,6-dimethyl-2(3-butynyl)cyclohexanone

Reaction: ##STR71## Procedure:

Under a nitrogen blanket in a 1 liter reaction flask is placed 39.9 g(1.02 moles) of sodamide in 200 ml toluene. With stirring, 43.8 grams ofthe 2,6-dimethyl-2(gamma-chlorocrotyl)cyclohexanone produced accordingto Part A in 200 ml toluene is added to the sodamide mixture and theresulting reaction mass is refluxed at 105°-110° C for a period of 12hours.

The reaction mass is then cooled to 0-5° C and 10% aqueous HCl (200 ml)is added and the reaction mass is then stirred for 10 minutes at roomtemperature. The reaction mass is then extracted with five 100 mlportions of diethyl ether and the ether extracts are combined, driedover anhydrous magnesium sulfate and evaporated yielding 47.0 g of acrude product which is distilled to yield 27.0 g of2,6-dimethyl-2(3-butynyl)cyclohexanone having the structure: ##STR72##

Part C: Production of 2,6-dimethyl-2,3(oxobutyl)cyclohexanone

Reaction: ##STR73## Procedure:

A mixture of 27 g of 2,6-dimethyl-2(3-butynyl)cyclohexanone, 91.8 mlwater, 6.7 g sulfuric acid (concentrated), 1.3 g mercuric sulfate and168 ml of methanol is stirred at room temperature for a period of 1.5hours. The resulting reaction mass is then extracted with five 100 mlportions of diethyl ether and the ether extracts are combined, driedover anhydrous sodium sulfate and evaporated to yield 28 g of2,6-dimethyl-2,3(oxobutyl)cyclohexanone having the structure: ##STR74##as confirmed by Infrared analysis.

Part D: Production of trans-8,10-dimethyl(9)octal-2-one

Reaction: ##STR75## Procedure:

A mixture of 27.0 g of 2,6-dimethyl-2,3-oxobutyl cyclohexanone isintimately admixed with 9.37 g of sodium ethoxide and 500 ml food gradeethyl alcohol and the resulting mixture is added under a nitrogenblanket for 1 hour at 45°-50° C. After the 1 hour period, 500 ml wateris added and the reaction mass is extracted with five 100 ml portions ofdiethyl ether. The combined ether extracts are washed with water to a pHof 7 and concentrated to yield 23.0 g of crude product.

This material is distilled to yield 16 g product, b.p. 70°-77° C (0.15mm Hg) having the structure: ##STR76##

Part E:

Reaction: ##STR77## Procedure:

Into a 2 liter reaction flask is placed 720 ml dioxane and acetylene ispassed into the dioxane for 1 hour. The solution is stirred as 123.28 g(1.34 moles) of lithium acetylide-ethylene diamine complex is added.12.0 g of the trans-8,10-dimethyl(9)octal-2-one produced according toPart D in 100 ml dioxane is then added to the reaction mass over aperiod of 30 minutes. Passage of acetylene gas into the reaction mass iscontinued for one hour after the addition. The reaction mass is thenstirred at room temperature, blanketed with nitrogen for a period of 24hours.

750 ml of saturated aqueous ammonium chloride solution is then addedslowly to the reaction mass and the organic layer is separated. Theaqueous phase is washed with diethyl ether and the ether extract andorganic layer are combined. The resulting solution is washed with wateruntil neutral, dried and concentrated to yield 24.0 g of a compoundhaving the structure: ##STR78##

Part F: Production of2-acetyl-3,4,4a,5,6,7-hexahydro-4a,8-dimethylnaphthalene

Reaction: ##STR79## Procedure:

24.0 g of the compound having the structure: ##STR80## is intimatelyadmixed with 160 ml 98% formic acid. The resulting mixture is refluxedfor 2 1/2 hours and then cooled to room temperature and neutralized withsaturated aqueous sodium bicarbonate. The resulting mixture is thenextracted with five 100 ml portions of diethyl ether. The ether extractsare washed with water until neutral and then concentrated. The resultingcrude material, on distillation, gives 1.5 g of material, b.p. 151-155(0.5 mm Hg); 2-acetyl-3,4,4a,5,6,7-hexahydro-4a,8-dimethylnaphthalenehaving the structure: ##STR81## as confirmed by NMR, Infrared and MassSpectral analyses. The NMR, Infrared and Mass Spectral data areidentical to those set forth in Example XII.

What is claimed is:
 1. A perfume composition having a vetiver charactercomprising (i) a composition of matter consisting of a mixture of threecompounds defined by the structure:wherein one of the dashed lines is acarbon-carbon double bond and each of the other of the dashed lines is acarbon-carbon single bond in an olfactorily effective amount and (ii) atleast one adjuvant selected from the group consisting of natural perfumeoils, synthetic perfume oils, alcohols, aldehydes, ketones other thanketones contained in said mixture (i), nitriles, esters and lactones. 2.A cologne composition comprising ethanol, water and a composition ofmatter consisting of a mixture of three compounds defined by thestructure: ##STR82## wherein one of the dashed lines is a carbon-carbondouble bond and each of the other of the dashed lines is a carbon-carbonsingle bond in an olfactorily effective amount, said cologne having avetiver character.